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Molecules (Basel, Switzerland) Oct 2022Innovative technologies can transform what are now considered "waste streams" into feedstocks for a range of products. Indeed, the use of biomass as a source of... (Review)
Review
Innovative technologies can transform what are now considered "waste streams" into feedstocks for a range of products. Indeed, the use of biomass as a source of biopolymers and chemicals currently has a consolidated economic dimension, with well-developed and regulated markets, in which the evaluation of the manufacturing processes relies on specific criteria such as purity and yield, and respects defined regulatory parameters for the process safety. In this context, ionic liquids and deep eutectic solvents have been proposed as environmentally friendly solvents for applications related to biomass waste valorization. This mini-review draws attention to some recent advancements in the use of a series of new-solvent technologies, with an emphasis on deep eutectic solvents (DESs) as key players in the development of new processes for biomass waste valorization. This work aims to highlight the role and importance of DESs in the following three strategic areas: chitin recovery from biomass and isolation of valuable chemicals and biofuels from biomass waste streams.
Topics: Biofuels; Biomass; Chitin; Deep Eutectic Solvents; Ionic Liquids; Solvents
PubMed: 36235144
DOI: 10.3390/molecules27196606 -
The Journal of Physical Chemistry. B Apr 2017Inhomogeneous solvation theory (IST) and classical density functional theory (DFT) each provide a framework for relating distribution functions of solutions to their... (Review)
Review
Inhomogeneous solvation theory (IST) and classical density functional theory (DFT) each provide a framework for relating distribution functions of solutions to their thermodynamic properties. As reviewed in this work, both IST and DFT can be formulated in a way that use two "end point" simulations, one of the pure solvent and the other of the solution, to determine the solute chemical potential and other thermodynamic properties of the solution and of subvolumes in regions local to the solute containing hydrating waters. In contrast to IST, where expressions for the excess energy and entropy of solution are the object of analysis, in the DFT end point formulation of the problem, the solute-solvent potential of mean force (PMF) plays a central role. The indirect part of the PMF corresponds to the lowest order (1-body) truncation of the IST expression. Because the PMF is a free energy function, powerful numerical methods can be used to estimate it. We show that the DFT expressions for the solute excess chemical potential can be written in a form which is local, involving integrals only over regions proximate to the solute. The DFT end point route to estimating solvation free energies provides an alternative path to that of IST for analyzing solvation effects on molecular recognition and conformational changes in solution, which can lead to new insights. In order to illustrate the kind of information that is contained in the solute-solvent PMF, we have carried out simulations of β-cyclodextrin in water. This solute is a well studied "host" molecule to which "guest" molecules bind; host-guest systems serve as models for molecular recognition. We illustrate the range of values the direct and indirect parts of the solute-solvent PMF can have as a water molecule is brought to the interface of β-cyclodextrin from the bulk; we discuss the "competition" between these two terms, and the role it plays in molecular recognition.
Topics: Quantum Theory; Solubility; Solutions; Solvents; Thermodynamics
PubMed: 28186751
DOI: 10.1021/acs.jpcb.6b12889 -
Journal of Pharmacy & Pharmaceutical... 2010N-Methyl-2-pyrrolidone (NMP) or Pharmasolve is very strong solubilizing agent and it has important applications in different fields of industry. This review presents NMP... (Comparative Study)
Comparative Study Review
N-Methyl-2-pyrrolidone (NMP) or Pharmasolve is very strong solubilizing agent and it has important applications in different fields of industry. This review presents NMP physicochemical characteristics, application especially in pharmaceutical sciences, pharmacokinetic and toxicity. Characteristics of NMP such as physicochemical properties, solubilization efficacy, toxicity and adverse effects were compared with other common solvents used in the pharmaceutical industries. This review reveals that NMP is an acceptable pharmaceutical solvent and its efficacy, toxicity, and side effects are comparable with other common solvent.
Topics: Animals; Excipients; Humans; Pharmaceutical Preparations; Pyrrolidinones; Solubility; Solvents
PubMed: 21486529
DOI: 10.18433/j3p306 -
Molecules (Basel, Switzerland) Apr 2020Polyelectrolytes in solution show a broad plethora of interesting effects. In this short review article, we focus on recent theoretical and computational findings... (Review)
Review
Polyelectrolytes in solution show a broad plethora of interesting effects. In this short review article, we focus on recent theoretical and computational findings regarding specific ion and solvent effects and their impact on the polyelectrolyte behavior. In contrast to standard mean field descriptions, the properties of polyelectrolytes are significantly influenced by crucial interactions with the solvent, co-solvent and ion species. The corresponding experimental and simulation results reveal a significant deviation from theoretical predictions, which also highlights the importance of charge transfer, dispersion and polarization interactions in combination with solvation mechanisms. We discuss recent theoretical and computational findings in addition to novel approaches which help broaden the applicability of simple mean field theories.
Topics: Biophysical Phenomena; Computer Simulation; Ions; Models, Chemical; Polyelectrolytes; Solvents
PubMed: 32260301
DOI: 10.3390/molecules25071661 -
International Journal of Molecular... Dec 2022In the panorama of sustainable chemistry, the use of green solvents is increasingly emerging for the optimization of more eco-friendly processes which look to a future... (Review)
Review
In the panorama of sustainable chemistry, the use of green solvents is increasingly emerging for the optimization of more eco-friendly processes which look to a future of biocompatibility and recycling. The green solvent Cyrene, obtained from biomass via a two-step synthesis, is increasingly being introduced as the solvent of choice for the development of green synthetic transformations and for the production of biomaterials, thanks to its interesting biocompatibility, non-toxic and non-mutagenic properties. Our review offers an overview of the most important organic reactions that have been investigated to date in Cyrene as a , in particular focusing on those that could potentially lead to the formation of relevant chemical bonds in bioactive molecules. On the other hand, a description of the employment of Cyrene in the production of biomaterials has also been taken into consideration, providing a point-by-point overview of the use of Cyrene to date in the aforementioned fields.
Topics: Solvents; Green Chemistry Technology; Biomass
PubMed: 36555601
DOI: 10.3390/ijms232415960 -
Chemical Reviews Mar 2022Dipolar aprotic and ethereal solvents comprise just over 40% of all organic solvents utilized in synthetic organic, medicinal, and process chemistry. Unfortunately, many... (Review)
Review
Dipolar aprotic and ethereal solvents comprise just over 40% of all organic solvents utilized in synthetic organic, medicinal, and process chemistry. Unfortunately, many of the common "go-to" solvents are considered to be "less-preferable" for a number of environmental, health, and safety (EHS) reasons such as toxicity, mutagenicity, carcinogenicity, or for practical handling reasons such as flammability and volatility. Recent legislative changes have initiated the implementation of restrictions on the use of many of the commonly employed dipolar aprotic solvents such as dimethylformamide (DMF) and -methyl-2-pyrrolidinone (NMP), and for ethers such as 1,4-dioxane. Thus, with growing legislative, EHS, and societal pressures, the need to identify and implement the use of alternative solvents that are greener, safer, and more sustainable has never been greater. Within this review, the ubiquitous nature of dipolar aprotic and ethereal solvents is discussed with respect to the physicochemical properties that have made them so appealing to synthetic chemists. An overview of the current legislative restrictions being imposed on the use of dipolar aprotic and ethereal solvents is discussed. A variety of alternative, safer, and more sustainable solvents that have garnered attention over the past decade are then examined, and case studies and examples where less-preferable solvents have been successfully replaced with a safer and more sustainable alternative are highlighted. Finally, a general overview and guidance for solvent selection and replacement are included in the Supporting Information of this review.
Topics: Chemistry, Organic; Dimethylformamide; Solvents
PubMed: 35201751
DOI: 10.1021/acs.chemrev.1c00672 -
The Journal of Physical Chemistry. B Sep 2023Protein/solvent interactions largely influence protein dynamics, particularly motions in unfolded and intrinsically disordered proteins (IDPs). Here, we apply...
Protein/solvent interactions largely influence protein dynamics, particularly motions in unfolded and intrinsically disordered proteins (IDPs). Here, we apply triplet-triplet energy transfer (TTET) to investigate the coupling of internal protein motions to solvent motions by determining the effect of solvent viscosity (η) and macromolecular crowding on the rate constants of loop formation () in several unfolded polypeptide chains including IDPs. The results show that the viscosity dependence of loop formation depends on amino acid sequence, loop length, and co-solute size. Below a critical size (), co-solutes exert a maximum effect, indicating that under these conditions microviscosity experienced by chain motions matches macroviscosity of the solvent. depends on chain stiffness and reflects the length scale of the chain motions, i.e., it is related to the persistence length. Above , the effect of solvent viscosity decreases with increasing co-solute size. For co-solutes typically used to mimic cellular environments, a scaling of ∝ η is observed, suggesting that dynamics in unfolded proteins are only marginally modulated in cells. The effect of solvent viscosity on in the small co-solute limit (below ) increases with increasing chain length and chain flexibility. Formation of long and very flexible loops exhibits a ∝ η viscosity dependence, indicating full solvent coupling. Shorter and less flexible loops show weaker solvent coupling with values as low as ∝ η. Coupling of formation of short loops to solvent motions is very little affected by amino acid sequence, but solvent coupling of long-range loop formation is decreased by side chain sterics.
Topics: Intrinsically Disordered Proteins; Solvents; Protein Folding; Viscosity; Peptides
PubMed: 37722681
DOI: 10.1021/acs.jpcb.3c04070 -
Molecules (Basel, Switzerland) Nov 2020The ever-growing interest in the cross-coupling reaction and its applications has increased exponentially in the last decade, owing to its efficiency and effectiveness.... (Review)
Review
The ever-growing interest in the cross-coupling reaction and its applications has increased exponentially in the last decade, owing to its efficiency and effectiveness. Transition metal-mediated cross-couplings reactions, such as Suzuki-Miyaura, Sonogashira, Heck, and others, are powerful tools for carbon-carbon bond formations and have become truly fundamental routes in catalysis, among other fields. Various greener strategies have emerged in recent years, given the widespread popularity of these important reactions. The present review comprises literature from 2015 onward covering the implementation of unconventional methodologies in carbon-carbon (C-C) cross-coupling reactions that embodies a variety of strategies, from the use of alternative energy sources to solvent- free and green media protocols.
Topics: Carbon; Catalysis; Chemistry Techniques, Synthetic; Ionic Liquids; Models, Chemical; Oxidative Coupling; Phase Transition; Solvents
PubMed: 33255429
DOI: 10.3390/molecules25235506 -
TheScientificWorldJournal 2014Lipases are a group of enzymes naturally endowed with the property of performing reactions in aqueous as well as organic solvents. The esterification reactions using... (Review)
Review
Lipases are a group of enzymes naturally endowed with the property of performing reactions in aqueous as well as organic solvents. The esterification reactions using lipase(s) could be performed in water-restricted organic media as organic solvent(s) not only improve(s) the solubility of substrate and reactant in reaction mixture but also permit(s) the reaction in the reverse direction, and often it is easy to recover the product in organic phase in two-phase equilibrium systems. The use of organic solvent tolerant lipase in organic media has exhibited many advantages: increased activity and stability, regiospecificity and stereoselectivity, higher solubility of substrate, ease of products recovery, and ability to shift the reaction equilibrium toward synthetic direction. Therefore the search for organic solvent tolerant enzymes has been an extensive area of research. A variety of fatty acid esters are now being produced commercially using immobilized lipase in nonaqueous solvents. This review describes the organic tolerance and industrial application of lipases. The main emphasis is to study the nature of organic solvent tolerant lipases. Also, the potential industrial applications that make lipases the biocatalysts of choice for the present and future have been presented.
Topics: Catalysis; Enzymes, Immobilized; Lipase; Organic Chemicals; Solubility; Solvents; Substrate Specificity
PubMed: 24672342
DOI: 10.1155/2014/625258 -
Journal of Proteome Research Nov 2022Proteomic analysis of absorbed residues is increasingly used to identify the foodstuffs processed in ancient ceramic vessels, but detailed methodological investigations...
Proteomic analysis of absorbed residues is increasingly used to identify the foodstuffs processed in ancient ceramic vessels, but detailed methodological investigations in this field remain rare. Here, we present three interlinked methodological developments with important consequences in paleoproteomics: the comparative absorption and identification of various food proteins, the application of a deep eutectic solvent (DES) for extracting ceramic-bound proteins, and the role of database choice in taxonomic identification. Our experiments with modern and ethnoarcheological ceramics show that DES is generally more effective at extracting ceramic-bound proteins than guanidine hydrochloride (GuHCl), and cereal proteins are absorbed and subsequently extracted and identifiedat least as readily as meat proteins. We also highlight some of the challenges in cross-species proteomics, whereby species that are less well-represented in databases can be attributed an incorrect species-level taxonomic assignment due to interspecies similarities in protein sequence. This is particularly problematic in potentially mixed samples such as cooking-generated organic residues deposited in pottery. Our work demonstrates possible proteomic separation of fishes and birds, the latter of which have so far eluded detection through lipidomic analyses of organic residue deposits in pottery, which has important implications for tracking the exploitation of avian species in various ancient communities around the globe.
Topics: Deep Eutectic Solvents; Proteomics; Archaeology; Proteins; Ceramics; Solvents
PubMed: 36268809
DOI: 10.1021/acs.jproteome.2c00340